Officials said at least two people were killed in an attack on a hotel in the central city of Kryvyi Rih and two more died in a wave of drone strikes on the Zaporizhzhia region in the south east.
Ukrainian monitors had earlier detected Russian aircraft launching hypersonic missiles and the air force said it had shot down five missiles and 60 drones.
It was learnt that at least six people died overnight Sunday to Monday and dozens were wounded as more than half of Ukraine’s regions were attacked by drones and missiles.
Power infrastructure was hit causing blackouts in many cities, with water supplies also affected.
A statement from the Russian defence ministry said long-range air and sea-based precision weaponry had been used to strike power stations and related infrastructure across Ukraine, including in Kyiv, Lviv and the Kharkiv and Odesa regions.
US President Joe Biden called the attacks outrageous, saying Washington would continue to support Ukraine’s energy grid while UK Foreign Secretary David Lammy condemned Russia’s cowardly missile and drone attacks on civilian infrastructure”.
In the latest attacks overnight into Tuesday, Russia said it had launched 10 missiles and 81 drones.
A hotel was struck by a ballistic missile in Kryvyi Rih late on Monday, killing a man and a woman and leaving several others wounded. Two people were reported missing.
Kryvyi Rih is the home city of Ukraine’s President Volodymyr Zelensky.
On Monday, Zelensky called on Western allies including the UK, the US and France to change their rules and let Ukraine use their weapons to strike deeper inside Russia.
Ukraine is allowed to use some Western weapons to hit targets inside Russia – but not long-range weapons.